The Effects of Dissolved Halide Anions on Hydrogen Bonding in Liquid Water

It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as “structure makers” and “structure breakers” has been based in part on corresponding changes in the...

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Veröffentlicht in:Journal of the American Chemical Society 2007-11, Vol.129 (45), p.13847-13856
Hauptverfasser: Smith, Jared D, Saykally, Richard J, Geissler, Phillip L
Format: Artikel
Sprache:eng
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Zusammenfassung:It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as “structure makers” and “structure breakers” has been based in part on corresponding changes in the vibrational spectra (Raman and IR). Here we show that changes in O−H vibrational spectra induced by the alkali halides in liquid water result instead from the actions of ions' electric fields on adjacent water molecules. Computer simulations that accurately reproduce our experimental measurements suggest that the statistics of hydrogen-bond strengths are only weakly modified beyond this first solvation shell.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja071933z